Method for controlling algae

ABSTRACT

COMPOUNDS HAVING THE FORMULA   BR-CH(-R)-COO-CH2-CH(-R2)-C*C-R1   IN WHICH R IS HYDROGEN OR CYANO, AND R1 IS HYDROGEN, ALKYL, ARYL, NUCLEAR SUBSTITUTED ARYL OR -CH2-OOC-CH(-R)-BR R2 IS H OR METHYL, THEIR EMTHOD OF PREPARATION, AND THE USE OF THESE COMPOUNDS AS BIOCIDES, SUCH AS IN CONTROLLING FUNGI, BACTERIA, AND ALGAE.

United States Patent 3,711,271 METHOD FOR CONTROLLING ALGAE Don R.Baker, Orinda, Calif., assignor to Staulfer Chemical Company, New York,N.Y. No Drawing. Filed Aug. 28, 1969, Ser. No. 853,950 Int. Cl. A01n9/00 US. Cl. 71-67 1 Claim ABSTRACT OF THE DISCLOSURE Compounds havingthe formula in which R is hydrogen or cyano, and R is hydrogen, alkyl,aryl, nuclear substituted aryl or R is H or methyl, their method ofpreparation, and the use of these compounds as biocides, such as incontrolling fungi, bacteria, and algae.

SUMMARY OF THE INVENTION This invention comprises novel compositions ofmatter, their method of preparation, and their use as biocides. Moreparticularly, the invention relates to compositions of matter having theformula in which R is hydrogen or cyano; R is hydrogen or methyl, themethod of preparation of these compositions, and the use of thesecompositions as fungicides, bactericides and algaecides.

DESCRIPTION OF PREFERRED EMBODIMENT In its most preferred form, thisinvention relates to compositions of matter having the formula wherein Ris selected from the group consisting of hydrogen and methyl, and R isselected from the group consisting of hydrogen, alkyl, especially methyland ethyl, and

the method of preparation of these compositions, and the use of thesecompositions as fungicides, bactericides and algaecides.

The term nuclear substituted includes both mono and poly substitutionwith the specified substituents.

3,711,271 Patented Jan. 16, 1973 Representative compounds of thisinvention are as follows:

l-bromoacetoxy-3-butyne l-bromoacetoxy-S-octyne1bromoacetoxyl-phenyl-3butyne l-bromoacetoxy-4- (p-chlorophenyl)3-butyne 1,S-bis-bromoacetoxy-B-pentyne l-u-bromocyanoacetoxy-3pentyne1bromoacetoxy-Z-methyl-3butyne While generally it is preferred that therespective R groups be identical in the compounds of the inventionhaving two reacted acyl moieties, it is not a requirement, and compoundswherein the reacted acyl moieties are different are within thecontemplation of the invention. The compounds of the present inventionare particularly useful in inhibiting the growth of bacteria, fungi andalgae.

The compounds of the present invention, except those in which R is maybe prepared by reacting a compound of the formula Compounds of theformula R o R Br-JJ-i-O-CH2CHR CEC-CHzO-g-Br 1'1 it in which R and R areas above defined can be prepared by reacting about 2 moles of a compoundof the formula wherein R is as above indicated, and hal is chlorine,bromine, or iodine, with a compound of the formula HO-CHzCHCEC-CHt-OHThe concentrations of the reactants employed are not particularlycritical, although generally a slight excess of the acetyl halide(reactant A) will be employed. A suitable concentration will be fromabout 1.0 mol to about 2.5 mols of monohydroxy compound (reactant B),although additional quantities may be present. Where the hydroxycompound (reactant B) is a diol, the acetyl halide should be present ona basis of from about 2.0 mols to about 3.5 mols per mol of diol. Apreferred range for monohydroxy compound reactants (reactant B) would befrom about 1.0 to about 2.5 mols of reactant A per mol of reactant B.Similarly, for diol compounds (reactant B), a preferred range ofconcentrations of reactant A should be from about 2.0 to about 3.5 mols,or greater, per mol of reactant (B).

The reactions are preferably carried out under anhydrous conditions inthe presence of a base such as pyridine or triethylamine and in asolvent for the reactants. Suitable solvents include ether, benzene,chloroform or tetrahydro-furan. Reactions of this type are normallyexothermic so that the addition of heat is not required. Inactuality,cooling may sometimes be required to control the reaction rate. Thereaction will normally be carried out at a temperature of from about C.to about 55 C. Pressures may be atmospheric, sub-atmospheric, or greaterthan atmospheric, as desired.

Preparation of the compounds of this invention is illustrated by thefollowing examples:

EXAMPLE I Preparation of l-bromoacetoxy-fa-butyne Approximately 91.3grams (1.3 moles) of 3-butyne-1- 01 is dissolved in chloroform andcooled to about C. About 134.6 grams (185.5 milliliters) oftriethylamine and 26 2.5 grams (1.3 moles) of bromoacetyl bromidediluted in chloroform to equal the volume of triethylamine are addedsimultaneously to the l-ol chloroform solution. The temperature is heldbetween 5 C. and C. during addition. After addition, the reactionmixture is stirred for about one hour and allowed to come to roomtemperature. The mixture is washed several times with water and driedover MgSO-g. The mixture is decolorized by stirring for about an hourwith activated charcoal, and is then concentrated by evaporation toyield 242.1 grams of liquid. N.M.R. spectra confirms the structure ofthe liquid.

EXAMPLE II Preparation of l,S-b-is-bromoacetoxy-3-pentyneSimultaneously, 80.8 g. of bromoacetyl bromide (0.4 mole) and 40.4 g. oftriethylamine (0.4 mole) are added to a stirred solution of 20.0 g. of3-pentyne-l,5-diol (0.2 mole) dissolved in 350 ml. of tetrahydrofuran.In order to facilitate the simultaneous addition, the volume of thebromoacetyl bromide is equalized to that of the triethylamine by theaddition of chloroform. The reaction temperature is maintained at 5-10"C. by external cooling. After the addition is complete, stirring iscontinued for one hour and the reaction allowed to come to roomtemperature. The resulting mixture is filtered and the filtrate isdiluted with an equal volume of benzene. The diluted filtrate is washedseveral times with Water and then dried over magnesium sulfate. Thedried solution is decolorized somewhat by stirring with activatedcharcoal. After removing the charcoal by filtration, the solution isconcentrated in vacuo.

EXAMPLE Ill Preparation of 1,5-bis(bromoacetoxy)-2-methyl-3-pentyne Theprocedure of Example II is repeated, using 22.8 grams of2-methyl-3-pentyne-l,S-diol instead of the 3- butyne-l-ol.

EXAMPLE IV Preparation of 1-bromoacetoxy-Z-methyl-Z-pentyne Theprocedure of Example I is repeated, utilizing 122 grams of2-methyl-3-pentyne-l-ol instead of the B-butynel-ol.

The following is a table of certain selected compounds that may beprepared according to the procedure described hereto.

TABLE I I ll nr-c i-o-o-on onrwozcqa R R hydrogen -CH 0C (O)CH Brhydrogen hydrogen methyl methyl hydrogen phenyl In order to demonstrateusefulness, the following tests were conducted using1-bromoacetoxy-3-butyne as exemplary of the compounds of the invention.

In vitro vial test.This test measures the bactericidal and fungicidalproperties'of a compound when in contact with a growing bacterium orfungus in an artificial medium. The test is conducted by partiallyfilling a 1- ounce vial with malt broth and a l-ounce vial with nutrientbroth. Next, the test compound is added to the vials at a certainconcentration, expressed in parts per million, and mixed with the broth.A water suspension of spores of the desired fungi is added to a vialwith malt broth and water suspension of cells of the desired bacteria(one organism per vial) is added to a vial with nutrient broth. Thevials are then sealed and incubated for one week; at this time the vialsare examined and the results recorded. The table below shows the resultswhen l-brornoacetoxy-B-butyne is tested by the in vitro vial test.

Fungi Bacteria Asperigillus Penicillt'um Staphyluccus niger itaticumaureus Escherichia Algaecidal screening test Suificientl-bromoacetoxy-B-butyne is diluted in acetone to give a 0.5% solutionwhich is then diluted into 20 milliliters of warm modified Jack MeyersAgar medium. The dilutions are such as to give concentrations of 1, 5,l0 and 5t) [Lg-/H1l. of the test compound in 20 x mm. petri dishes.After the agar solidifies, each petri dish is inoculated with organismsof Scenedesmus obliquus and Chlorella pyrenoidosa. The samples were thenallowed to grow at room temperature under fluorescent lamps using a 14hour light period each day. After two weeks, the results are recorded asset forth in the table below:

TABLE III Scenedesmus Chlorella Conc. oblzqmre pyrenoidosa As can beseen by the test results, the compositions of the invention may be usedin killing bacteria, algae, and fungi. The compositions may be applieddirectly to the particular undesired biological organism or may beapplied to a locus to be protected. In either event, it is of coursenecessary that the unwanted organism receive an effective dosage oramount, i.e., an amount sufficient to kill or retard growth. Thecompositions may be applied to or in textiles, leather, paint, soaps,paper, wood, plastic, oil, and any other substances susceptible ofgrowth of undesirable biological organisms.

The compositions are normally employed with a suitable carrier and maybe applied as a dust, spray, drench or aerosol. The compositions thusmay be applied in combination with solvents, diluents, various surfaceactive agents (for example detergents, soaps or other emulsifying orwetting agents, surface active clays) carrier media, adhesives,spreading agents, humectants and the like. They may also be combinedwith other biologically active compositions, including other fungicides,bactericides, and algaecides, insecticides, growth stimulators,acaricides, herbicides, mollusicides, etc., as well as with fertilizers,soil modifiers, etc. The compositions of the invention may be used incombination with an inert carrier and a surface active or emulsifyingagent, and may also be applied in combination with other biologicallyactive materials, in conjunction with a carrier and a surface active oremulsifying agent. The solid and liquid formulations can be prepared byany of the conventional methods well-known by those skilled in the art.Since the amount of active agent required will vary according to thebiological organism treated, precise limits on the amounts employedcannot be given. Determination of the optimum effective concentrationfor a specific application is readily conducted by routine procedures,as will be apparent to those skilled in the art. As indicated, theamount applied in a given case will be an effective amount, i.e., anamount sufiicient to give the type of control desired.

Various changes and modifications may be made without departing from thespirit and the scope of the invention described herein, as will beapparent to those skilled in the art to which it pertains.

I claim:

1. A method of killing algae comprising applying thereto an aglaecidallyeffective amount of a compound having the formula 2,9 '1,754 4/1950Baldridge 71-106 X JAMES O. THOMAS, JR., Primary Examiner US. Cl. X.R.

